Durability of isocyanate resin adhesives for wood IV: degradation under constant steam heating

The durability of isocyanate resins consisting of emulsion-type polymeric diphenylmethane diisocyanate (EMDI) was investigated under constant steam heating. Two kinds of resin, water only-added resin and polyol/water-added resin, were used in this study. The degradation of the resins under steam heating was observed using Fourier transform infrared spectroscopy (FT-IR), weight changes, and thermogravimetric analysis (TGA). FT-IR analysis showed that the degradation reaction of the resins scarcely proceeded for a few hours and then increased significantly. The weights of the resins decreased linearly during steam heating. The thermal stability of steam-treated resins was made clear by TGA. The bond strength reductions of the specimens bonded with the resins were also observed. The best fitting regression function for the behavior of bond strength reduction was determined statistically. The apparent activation energy of each resin was calculated from the regression function, for the half-life period. Considering the calculated values, the adhesion durability of using polyol-added resin was superior to that of using water only-added resin. It was clarified that the durability of the isocyanate resins under steam heating was markedly inferior to that under dry heating.Part of this paper was presented at the 50th Annual Meeting of the Japan Wood Research Society, Kyoto, 2000     

Durability of isocyanate resin adhesives for wood III: degradation under constant dry heating

The durability of isocyanate resins consisting of emulsion-type polymeric diphenylmethane diisocyanate (EMDI) was investigated under constant dry heating. Two kinds of resin, water only-added resin and polyol/wateradded resin, were used in this study. The kinetic studies based on the weight losses of the resins were carried out by isothermal thermogravimetry (TG) at temperatures ranging from 260° to 320°C. The apparent activation energies of the resins were calculated for weight losses of 5%, 10%, and 15%. The values of apparent activation energy of the resins increased with increasing weight loss. The bond-strength reductions of the specimens bonded with the resins were observed at various temperatures from 120° to 180°C. The best-fitting regression function for the behavior of bond-strength reduction was determined statistically. The apparent activation energy of each resin was calculated from the regression function for the half-life period. According to the calculated values, the adhesion durability of polyol/wateradded resin was superior to that of water only-added resin. To speculate on the changes in weight loss and the chemical structure of the resins in the glue lines under dry heating, changes in the cured resins were also observed.Part of this paper was presented at the 49th Annual Meeting of the Japan Wood Research Society, Tokyo, 1999     

Durability of isocyanate resin adhesives for wood I: Thermal properties of isocyanate resin cured with water

The thermal properties of isocyanate (IC) resin cured with water were studied using dynamic mechanical analysis (DMA) and Fourier transform infrared spectroscopy. The thermal properties of cured phenol formaldehyde (PF) resin were also studied for comparison purposes. The DMA specimens were prepared using a unique technique. The relation between the mechanical and chemical changes of the resin during DMA was clarified. The cured PF resin had better thermal stability than the IC resin cured with water. The improvement of thermal stability in cured IC resin by heat treatment was considered to be less effective. The effect of the heating rate on the mechanical properties was also investigated. The apparent activation energy in the thermal degradation of cured IC resin was calculated based on the results obtained.Part of this paper was presented at the 47th Annual Meeting of the Japan Wood Research Society, Kochi, April 1997     

Durability of isocyanate resin adhesives for wood V: changes of color and chemical structure in photodegradation

The effect of ultraviolet (UV) light irradiation on the color and chemical structure of water-cured polymeric diphenylmethane diisocyanate (PMDI) was investigated using a UV long-life fade meter. Control treatment was performed without UV light irradiation using a thermohygrostat for comparison. Two kinds of resin were used in this study: that to which only water had been added, and resin to which a small amount of polyol and water had been added. In addition, lauan (Shorea spp.) wood was used as a reference. The photodegradation of the resins over a period of up to 300 h was observed using a colorimeter and Fourier transform infrared (FT-IR) spectroscopy. When the resins were treated with UV light, the color difference (ΔE ^* ab) of the resins increased signifi cantly in a short time, and then reached a near-constant value. For lightness, L ^* decreased rapidly for a few hours and then decreased gradually. The color darkened compared with that of the wood used. When treatment was performed without UV light irradiation, ΔE ^* ab and ΔL ^* of the resins showed negligible change. Based on the results of FT-IR analysis, severe degradation such as cleavage of the main chemical bond was hardly observed under UV light irradiation irrespective of the type of resin. Part of this report was presented at the 54th Annual Meeting of the Japan Wood Research Society, Sapporo, Japan, and at the 6th International Wood Science Symposium, Bali, Indonesia     

Efficacy of polymeric MDI/Polyol mixtures for binding wood boards

Components of polyurethane synthesis are tested for their ability to bind pine wood into boards and are compared to the efficiency of using only the isocyanate component of polyurethane synthesis. A variety of polyols are tested varying equivalent weight, functionality, reactivity as determined by the availability of primary hydroxyl endgroups, and viscosity. The boards are fabricated at a variety of densities and under a variety of conditions. The results show that board properties using only the isocyanate component are always superior to those including a polyol component, but the board properties are not always a simple function of the amount of isocyanate put in the board. Furthermore, it is observed that the lower the room temperature surface tension between the polyol and isocyanate, the better the measured board properties; but, the higher the observed surface tension, the better the board will self-release from the metal caul plates.     

氢化萜烯马来酸酐与环氧树脂固化物的性能研究

研究了氢化萜烯马来酸酐(HTMA)与环氧树脂固化物的机械强度、热稳定性及电气绝缘等性能及其主要影响因素.实验结果表明,采用氢化萜烯马来酸酐固化后的环氧树脂具有较好的机械强度、热稳定性及电气绝缘性能.氢化萜烯马来酸酐的化学结构与固化物的机械强度及热稳定性密切相关.不同化学结构脂环酸酐固化后的环氧树脂电气绝缘性能相近.     

脲醛树脂分子量分布与胶合性能关系的研究（续）：分次加尿素对脲醛树？…

主要探讨分次加尿素对脲醛树脂分子量分布及胶合性能的影响。研究结果表明：在脲醛树脂合成吕，分次加入尿素，不仅可起到降低胶中游离醛的作用，同时还可起到分子量的调解作用。尤其是加入第２次尿素时，对胶中大分子部分可起到降解重排、减少胶中醚键含量的作用，从而达到低毒的目的。加入第２次尿素时，可能会改变脲醛树脂的反应机理。     

没食子酸改性氢化萜烯基环氧树脂多元醇的合成及性能研究

利用天然可再生资源没食子酸(GA)与氢化萜烯基环氧树脂(HTME)在一定条件下反应制备了环氧树脂基多元醇(HTME - GA多元醇).通过研究合成反应的影响因素,确定了HTME - GA多元醇的合成反应条件:以GA物质的量12.5倍的正丙醇为反应溶剂,以占HTME与GA总质量2%的季铵盐为催化剂,HTME与GA共沸回流反应3h.经FT - IR、NMR光谱表征了HTME - GA多元醇的化学结构,比较了该多元醇与聚己二异氰酸酯HN90T、改性聚己二异氰酸酯EC385的交联反应特性及交联产物性能.实验结果表明,HTME - GA多元醇与EC385的交联产物具有优良的机械力学性能,与HN90T的交联产物具有较好的耐液体介质性能和硬度,但后者柔韧性较差.随着NCO与OH物质的量比的增大,交联产物的硬度和耐液体介质性能提高.     

马来海松酸型聚氨酯烘漆耐热性研究

以马来海松酸酯多元醇为原料，制备了马来海松酸型聚氨酯烘漆，利用热重法，讨论了不同原料组分及配比，固化温度和固化时间等因素对烘漆耐热性的影响，另外，还利用ＤＳＣ，对二月桂酸二丁基锡对封闭异氰酸酯组分热解封温度的影响了讨论。     

阴离子型聚硅氧烷改性萜烯基环氧树脂多元醇水分散体的制备、表征及微观结构

以萜烯基环氧树脂(TME)与新戊二醇(NPG)反应,合成了萜烯基环氧树脂基多元醇(T-N),再以端羟丙基聚硅氧烷(HTP)、2,4-甲苯二异氰酸酯(TDI)及2,2-二(羟甲基)丙酸(DMPA)改性T-N,制备了阴离子型聚硅氧烷改性萜烯基环氧树脂多元醇(T-N-S)水分散体,并以红外光谱(FT-IR)、核磁共振光谱(NMR)表征了多元醇的化学结构。研究了反应条件、改性剂HTP用量等对多元醇水分散体稳定性及微观结构的影响。结果表明:DMPA与TDI物质的量比为1∶2,丙酮为溶剂(用量为反应物总质量的1.5~2倍),丙酮回流温度(56℃)下反应3 h,再加入T-N及HTP,继续反应4 h,所合成的T-N-S能够较好地在水中分散。透射电子显微镜分析表明,当HTP用量为T-N质量的3%~12%时,制备的T-N-S水分散体粒子均为球形粒子,粒径范围100~300 nm。     

丙烯海松酸聚氧乙烯酯聚醚多元醇的合成研究

研究了丙烯海松酸与不同摩尔数的环氧乙烷所进行的开环均聚和共聚反应。探讨了不同因素对反应速度及环氧乙烷聚合度对产物性能的影响，分析了产物的红外光谱及热重曲线。结果表明，该聚醚多元醇可作为一种新型多元醇应用于聚氨酯涂料中。     

水性异氰酸酯交联剂的应用研究

采用不同链长的聚醚多元醇与多亚甲基多苯基多异氰酸酯（PAPI）反应,制备了两种不同结构的水性异氰酸酯（P-C、P-D）,联剂分别加入到氧化玉米淀粉胶黏剂和脲醛树脂胶黏剂中,以改善胶黏剂的胶接性能。通过粘接强度测试研究不同结构、不同用量的水性异氰酸酯对改性胶黏剂的胶接强度和耐水性的影响。实验结果表明：氧化玉米淀粉和脲醛树脂中加入水性异氰酸酯交联剂制备胶合板,胶接强度及耐水性均有显著提高。氧化玉米淀粉胶黏剂中加入10%的水性异氰酸酯P-D后,所制备胶合板的干态剪切强度可达2.64MPa。脲醛树脂胶黏剂中加入7.5%的P-D后,干态、湿态剪切强度分别为1.24MPa和1.23MPa,甲醛释放量为0.31mg/L,达到E0级标准。     

Comparison of protein-based adhesive resins for wood composites

The search for new value-added uses for oilseed and animal proteins led us to develop protein-based wood adhesives. Low-fat soy and peanut flours and blood meal were hydrolyzed in an alkaline state, and PF-cross-linked protein resins were formulated by reacting the protein hydrolyzates with phenol-formaldehyde (PF) in solid-tosolid ratios ranging from 70% to 50% hydrolyzates and 30% to 50% PF. Physical properties of medium density fiberboard (MDF) bonded with protein-based phenolic resins were compared to those of boards bonded with ureaformaldehyde (UF) and PF resins, and flakeboard bonded with soy protein-based phenolic resin was compared to PF-bonded board. As MDF binders, adhesive properties of protein-based phenolic resins depended upon protein content of proteinacious materials. MDF board bonded with blood-based phenolic resin was comparable to PF-bonded board and met the requirements for exterior MDF. Boards bonded with soy-protein-based phenolic resin met requirements for interior MDF, while peanut-based phenolic failed to meet some of the requirements. Flakeboard bonded with soy-protein-based phenolic resins was inferior to PF-bonded board but outperformed PF-bonded board in accelerated aging tests. Although they exhibit a slow curing rate, the cost effectiveness and superior dimensional stability of protein-based phenolic resins may make them attractive for some uses.     

Influence of the melamine content in melamine-urea-formaldehyde resins on formaldehyde emission and cured resin structure

The effect of melamine content in melamine-urea-formaldehyde (MUF) resins on the formaldehyde emission and resin structure was investigated using six MUF resins synthesized with different F/(M + U) and M/U molar ratios. The formaldehyde emission from the plywood decreased as the F/(M + U) molar ratio decreased and the M/ U molar ratio increased. In addition, the bond performance was enhanced as the M/U molar ratio increased in the MUF resins with a fixed F/(M + U) molar ratio. Quantitative solution¹³C-NMR spectra of MUF resins revealed that the MUF resins with a high melamine content consisted of more highly branched crosslinkage structure and free melamine compared to the resins with low melamine contents. Furthermore, solid-state¹³C CP-MAS NMR spectra of cured MUF resins proved that more methylol groups, dimethylene ether, and branched methylene structures were present in the MUF resins with a higher F/(M + U) molar ratio, leading to increased bond strength and formaldehyde emission. There is no significant difference in the linkage structure of the cured resins with the same F/(M + U) and different M/U molar ratios except the ratios of carbonyl carbon of urea and triazine carbon of melamine. Therefore, the lower formaldehyde emission from cured MUF resins with a higher M/U molar ratio might be ascribed to the stronger linkages between triazine carbons of melamine than those of urea carbons. Consequently, the melamine contributed to strong crosslinking linkages in the cured resin structures, leading to lower formaldehyde emission and better bond performance.Part of this work was presented at the 48th Annual Meeting of the Japan Wood Research Society, Shizuoka, April 1998     

阳离子型萜烯基环氧树脂多元醇的合成及其分散稳定性研究

利用二乙醇胺(DEA)、聚乙二醇200(PEG200)对氢化萜烯 - 马来酸酐缩水甘油酯型环氧树脂(HTME)改性,制备了阳离子型环氧树脂基多元醇水分散体.通过对合成反应影响因素分析,确定了制备环氧树脂基多元醇的最佳反应条件:DEA用量为12%(以HTME的质量计,下同),PEG200与HTME(与DEA氨基反应后的量)物质的量比为1: 1 ～ 1.2: 1;催化剂ZnCl_2用量为2%,在100℃下反应6 ～ 7h.通过化学分析和红外光谱分析方法表征了该多元醇的化学结构.随着PEG200用量的增加,所合成多元醇的羟值提高,软化点、玻璃化温度(T_g)及分散体黏度降低.纳米粒度及电位分析表明,在酸性条件下,DEA用量为12%时所合成的环氧树脂基多元醇具有良好的水分散稳定性,水分散体的Z均粒径小于100nm.多元醇水分散体在高固含量时黏度较大,添加适量极性惰性稀释剂丙二醇甲醚醋酸酯可有效降低分散体黏度.     

甘蔗渣多元醇制备聚氨酯硬泡的研究

通过对甘蔗渣进行热化学液化,制得了以甘蔗渣多元醇为原料的硬质聚氨酯泡沫,主要讨论了催化剂、表面活性剂、发泡剂和异氰酸酯对其性能的影响。结果表明:催化剂B的用量为2.53%时,泡沫体的密度最小,但对泡沫的压缩模量的影响并不大;随着催化剂D用量的增加,泡沫密度和力学性能同时降低;表面活性剂AK-8805用量为2.06%时,泡沫的密度最小,其力学性能也比较好;以水为发泡剂,当水用量增加时,泡沫密度减小但力学性能没有随密度的减小而相应降低,而先有所增加,最后维持在一个平台上;异氰酸酯用量少了,反应程度不够,性能必然会降低,但用量加多了,同样会影响性能。研究表明,PM-200用量在220%~240%泡沫压缩性能最好。     

三乙醇胺改性沙柳液化产物/异氰酸酯硬质泡沫材料研究

生物质多元醇液化产物与异氰酸酯等反应可制备硬质聚氨酯泡沫材料,而该类材料存在力学性能低、脆性大等缺点,使其应用领域受到限制.以沙柳多元醇液化产物为原料,与异氰酸酯(MDI)等共聚制备沙柳液化产物/异氰酸酯硬质泡沫材料(RPUF),研究添加不同质量分数交联剂三乙醇胺(TEOA)对RPUF物理力学、化学结构和热学特性的影响...     

Curing behavior and adhesion properties of epoxy resin blended with polyhydric alcohol-liquefied <Emphasis Type="Italic">Cryptomeria japonica</Emphasis> wood

Cryptomeria japonica (Japanese cedar) wood was liquefied using polyethylene glycol (PEG-400 and PEG-600)/glycerol as the solvent with H₂SO₄ as a catalyst. The blended epoxy resins were prepared by mixing the liquefied wood with epoxy resin of various weight ratios and used for wood gluing. The results showed that blended epoxy resins could cure under room temperature with an exothermic reaction. DSC thermoanalysis showed that increasing the blending amount of liquefied wood would shift the peak of curing reaction to a higher temperature but with less heat released. Blended epoxy resins had a good dry bonding strength for wood when cured at room temperature. However, curing with heat treatment could improve the wet bonding strength of blended epoxy resins, especially for those prepared with PEG-400-liquefied wood.     

腰果酚二醚曼尼希碱固化剂的合成及其相分离现象研究

腰果酚(CD)和1,3-二溴丙烷经Williamson醚化反应得到一种腰果酚二醚化合物(CDE),然后以CDE、多聚甲醛和二乙烯三胺为原料,经Mannich反应制备得到一种浅色的腰果酚二醚曼尼希碱固化剂(MBCDE)。通过傅里叶红外光谱(FT-IR)和核磁共振氢谱(~1H NMR)表征了产物的化学结构,并与氨乙基哌嗪(AEP)进行对比研究其相关性能。通过热重分析(TGA)、扫描电镜(SEM)和力学性能测试研究了两种固化剂与双酚A环氧树脂(DGEBA)固化材料的相关性能。结果表明:MBCDE/DGEBA的最大分解温度为351.6℃,具有良好的热稳定性。AEP/DGEBA环氧固化物的冲击强度为3.641 J/m,而添加80%的MBCDE后固化物的冲击强度则为5.155 J/m,提高了41.6%。SEM分析结果表明MBCDE固化材料中存在相分离。     

Formaldehyde emission and high-temperature stability of cured urea-formaldehyde resins

A test method for measuring formaldehyde from urea-formaldehyde (UF) resins at high temperature was developed and used to assess the influence of the reaction pH on the formaldehyde emission and heat stability of the cured resins. Additionally, solid-state¹³C CP/MAS nuclear magnetic resonance (NMR) techniques were used to investigate the structure of cured UF resins before and after high temperature heating. Formaldehyde emissions during the cure were related to the UF resins' methylol group content. The heat stability of cured UF resins synthesized under strongly acidic conditions was much higher than that of the other resins, which were prepared in weakly acidic and alkaline media. Solid-state¹³C CP/MAS NMR spectra showed that formaldehyde emission from cured UF resins after heating is mainly ascribable to decreased methylol groups and dimethylene ether linkages. Significantly, it was revealed that uron structures characteristically found in the cured UF resin synthesized under strongly acidic medium indicated high heat stability.Parts of this paper were presented at the 44th annual meeting of the Japan Wood Research Society, Nara, April 1994; and at the 52nd annual meeting of the Forest Products Society, Merida, Mexico, June 1998